DE2608002C2 - - Google Patents

Description

The invention relates to aluminum-containing mixtures that can be used as paint driers.

It is known that an aluminum compound general formula

(RO) _x AlAB _{(2- x)}

where x is the number 0, 1 or 2, R is an alkyl group or a substituted alkyl group having 1 to 6 carbon atoms, an aryl group or a cycloalkyl group and A and B, which may be the same or different, each an alkoxide radical, a substituted alkoxide Radical, an aryl oxide radical, a substituted aryl oxide radical, an acyl oxide radical, a substituted acyl oxide radical, a carboxylic acid radical, a half ester radical or a group of the formula OMX, where M is a divalent metal and X is one Alkoxy, aryl oxide or acyl oxide residue, gelled when a molar deficit of the compound is added to an oil-modified alkyd resin or oil resin medium. In this process, gelation of the oil-modified alkyd resin or oil resin medium occurs.

In German Offenlegungsschrift 23 15 091 there is one stable compound or composition of the general formula

or a combination of I and II, in which A, B and C may be the same or different and are each selected from an alkoxy group, a substituted alkoxy group, an aryloxy group, a substituted aryloxy group, an alkycarboxyl group, a substituted alkycarboxyl group, an arylcarboxyl group, a substituted aryl carboxyl group, a derivative of a dicarboxylic acid in which only one carboxyl group is available for direct binding to aluminum, an alkyl sulfate, an aryl sulfonate, a dialkyl phosphate, a dialkyl phosphite, a diaryl phosphite or a group of the formula OMA ', in which O is an oxygen atom , M is a divalent metal and A 'as defined above A with the exception of the group OMA', x is the number 2 or more and Z is an organic polymer, an organic polycondensate or an inorganic particulate material, such as. B. a pigment or filler, a metal or mixtures thereof, which contains reactive groups or is able to form reactive groups by releasing hydrogen atoms on its surface.

In German Offenlegungsschrift 24 02 039 there is a Product described by combining an aluminum compound the general formula

(RO) _x AlAB _{(2- x)}

where x is the number 0, 1 or 2, R is an alkyl group with 1 to 6 carbon atoms, an aryl group or a cycloalkyl group and A and B, which may be the same or different, a half-ester residue, a branched-chain carboxylic acid residue with 3 or means more carbon atoms or an unsaturated fatty acid group having 3 or more carbon atoms, with at least 1 mole of a labile monofunctional reactant, which is an organic monohydroxy compound of the formula R¹OH, wherein R¹ represents a substituted or unsubstituted alkyl or cycloalkyl group in which the Alkyl or cycloalkyl radical containing 1 to 6 carbon atoms has been obtained.

Prevent the labile monofunctional reactants by reacting preferentially, complex formation, which occurs when aluminum compounds on oil modified Alkyl resins containing reactive groups such as hydroxyl and Carboxyl, are included. It is believed, that in the presence of the labile monofunctional reactant there is a balance that is disturbed when the oil modified alkyd resin on a surface is applied, making the unstable monofunctional Reactant by hydrolysis or by its own Volatility is released. The balance can go through the following equation can be represented:

The paint drying agents of the above mentioned German ones Laid open 24 02 039 must have at least 1 g-mole of labile monofunctional reactants per g-atom of aluminum included to the desired property of  Achieve shelf life when used in paint formulations be used.

The registration is based on the task, starting from that known from German laid-open specification 24 02 039 State of the art to provide mixtures those regarding their storage stability and drying properties have optimized results without the Quality of those obtained with the paint drier Adversely affect coatings.

This problem is solved in that the German Laid open 24 02 039 defined "labile monofunctional reactant "in whole or in part Water, aqueous hydrogen peroxide or an organic Hydroperoxide is replaced.

The present invention accordingly relates to Mixture of substances defined in claim 1.

According to a preferred embodiment, as Component (B) water alone or in a mixture with the organic monohydroxy compound of the formula R²OH used, wherein R² has the meaning given in claim 1 owns. The compound R²OH is at ambient temperatures preferably volatile.

From the unsubstituted organic Monohydroxy compounds R²OH can be primary alcohols, such as methanol, ethanol, butanol and oleyl alcohol, secondary Alcohols, such as sec-butanol, branched alcohols, such as Isopropanol and isobutanol, and cycloalcohols, such as Cyclohexanol can be used, the branched Alcohols are preferred.  

Among the substituted organic monohydroxy compounds R²OH are the alkoxy alcohols, such as ethoxyethanol, prefers. Other suitable connections are Diacetone alcohol, dialkyl alcohols, such as neopentanol, Trialky alcohols and alkyl ethers of glycol. Besides, can the enol form of labile tautomeric compounds, such as Acetylacetone, ethyl acetoacetate, lauryl acetoacetate and Ethylhexylacetoacetate can be used, which is of special The advantage is when a higher resistance to hydrolysis is required as it is easily unstable with others Substituents, such as ethoxyethanol, can be achieved.

If water or hydrogen peroxide without one Monohydroxy compound R²OH used as component (B) the water or the hydrogen peroxide preferably added an aluminum compound in which a tautomeric ketoenol residue is present.

Among the hydroperoxides used as component (B3) are t-butyl hydroperoxide and Cumene hydroperoxide preferred.

The mixtures according to the invention can be used in a broader range Range of paint media are used as those in the German laid-open specification 24 02 039, especially in media with high functionality that together with those in the German published application 24 02 039 products described for storage Tend to gel. This tendency to gel formation is still intensified by increasing the concentration of the Painting media in the non-reactive Solvents.

The components (A) in the mixtures according to the invention The aluminum compound used is a compound of  general formula

(RO) _x AlAB _{(2- x)}

where x is the number 0, 1 or 2, R is an alkyl group, a substituted alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkaryl group, an aminoalkyl group or a glycol half ester group, A and B, which may be the same or different , the same group as RO or a β- ketocarboxylic acid ester residue, a half ester residue, such as. B. a phthalate half-ester residue or a maleate half-ester residue, a diester residue, such as. B. mean a malonic diester residue, a carboxylic acid or amino carboxylic acid residue.

Aluminum compounds (A) are preferably used, in where RO is as defined above, but where A and B are the may be the same or different, each a half ester residue, a branched chain Carboxylic acid residue with 3 or more carbon atoms or one unsaturated fatty acid group with 3 or more Mean carbon atoms.

Aluminum compounds (A) used with preference are alkoxides, such as aluminum triisopropoxide and the mono-, di- and tri-substitution products, in which, for example, radicals are used which are derived from the following compounds:
Ethoxyethanol, butoxyethanol, cyclohexanol, 2-ethylhexanoic acid (2-ethyl-caproic acid), 3,5,5-trimethylhexanoic acid (3,5,5-trimethyl-caproic acid), versatic acid (mixture of synthetic fatty acids), naphthenic acid, acidic monoisopropyl phthalate and acidic monoethoxyethoxymaloxylate .

The mixtures according to the invention can be obtained by adding Water, hydrogen peroxide or organic Hydroperoxides or a mixture of water, Hydrogen peroxide or organic hydroperoxides and the organic monohydroxy compound R²OH to the Aluminum compound, even in a diluent can be solved, are produced, which is the Diluent either an inert material, such as. B. White spirit or one or more of the above Monohydroxy compounds R²OH can act. examples for other inert diluents, both volatile and non-volatile that can be used are xylene, Hydrocarbons and chlorinated hydrocarbons.

Alternatively, the water, hydrogen peroxide or the organic hydroperoxides together with the Monohydroxy compound R²OH, both in an inert Solvents are included, the aluminum compound be added.

The invention is illustrated by the following examples explained.

example 1

Aluminum isopropoxide 204 parts by weight Ethyl acetoacetate 130 parts by weight Wasser54 parts by weight White spirit287 parts by weight Aluminum content (as metal) 4% Molar ratio H₂O: Al3: 1  

Example 2

Aluminum triethoxy ethoxide 294 parts by weight Äthoxyäthanol363 parts by weight Water 18 parts by weight Aluminum content (as metal) 4% Molar ratio H₂O: Al1: 1

Example 3

Aluminum Diethoxyäthoxydmonoäthylacetoacetat334 parts by weight Water 36 parts by weight White spirit305 parts by weight

Example 4

Aluminum triethoxy ethoxide 294 parts by weight Ethyl acetoacetate 130 parts by weight Water 54 parts by weight chlorinated paraffin wax 225 parts by weight Äthoxyäthanol182 parts by weight Aluminum content (as metal) 3% Molar ratio H₂O: Al3: 1

Comparative Experiment I

For comparison, the two used in Example 3 Moles of water replaced by 2 moles of ethoxyethanol, taking one received the following preparation:

Monoethylacetoacetate 334 parts by weight Ethoxyethanol 180 parts by weight White spirit161 parts by weight Aluminum content (as metal) 4% Molar ratio H₂O: Al0

Example 5

Aluminum isopropoxide 204 parts by weight Ethyl acetoacetate 130 parts by weight 30% aqueous hydrogen peroxide 55 parts by weight White spirit286 parts by weight Aluminum content (as metal) 4% Molar ratio H₂O: H₂O₂: about 2: 0.5: 1

Example 6

Aluminum Diethoxyäthoxid-monoäthylacetoacetat344 parts by weight t-Butyl hydroperoxide (70% solution in di-t-butyl peroxide 128 parts by weight White spirit213 parts by weight Aluminum content (as metal) 4% Molar ratio of hydrogen peroxide: Al1: 1

The in Examples 1 to 6 and Comparative Experiment I Mixtures described were together with pigmented and non-pigmented alkyl media used and related for their durability and their drying properties compared to media in which conventional cobalt, Manganese, calcium and zirconium desiccants are used Comparative experiment I was a preparation  represents that within the framework of that in German Patent Application 24 02 039 invention falls.

The unpigmented one used in Table I. Paint medium was a 50% solution of one oil-modified alkyd resin based on pentaerythritol and phthalic anhydride containing one semi-drying oil corresponding to 65% of the weight of the Alkyd resin, expressed as linoleic acid, in white spirit. In terms of drying properties, the water was Example 3 containing slightly better than that of water free comparison test I if both with a content of Al of 1.5% on the alkyd solids were used, and both were superior to conventional Co / Ca / Zr.

Table II shows the drying effect of the mixtures of Example 3 and Comparative Experiment I with each other compared when combined with a titanium dioxide pigmented alkyl medium over a longer oil chain length a temperature range and over a range of relative humidity (RH) and at the same Al / alkyd ratio of 1.5% were used.

Table III shows the drying effect and the Resistance to the products of Examples 1 and 5 is due, compared with each other and this shows how by using cobalt and, in one to a lesser extent, by using manganese Resistance of the alkyd medium is impaired contains the substance mixture of Example 5, in which the Peroxide substituent has been incorporated. It also shows the advantages in terms of drying properties 100 ° C, which can be achieved by Example 5.  

Table IV shows the drying effect of the examples 3 and 6 when used with a long chain Oil alkyd resin and the influence of use and Not using cobalt and manganese drying agents on the shelf life of the unpigmented medium compared with each other. It can be seen from this that the Example 6 in combination with cobalt the best Drying properties, but poorer Storage stability results. Under drying conditions become the best drying properties and the best Film properties obtained when the mixture of the example 6 alone with 2% Al, based on the alkyd solids, is used.

The exemplary preparations given above point to those in the German patent application 24 02 039 optimized preparations Properties regarding storage and drying.

The drying preparations of Examples 1 to 4 paint formulations containing also persisted 6 months of storage while maintaining its low viscosity the viscosity of the desiccant according Comparative experiment I containing a formulation Period of 3 weeks and to form a loose gels.  

Table I

Non-pigmented 62% soy / pentaerythritol / alkyd 50% solids, applied in a wet film thickness of 0.0076 cm and dried at 20 ° C and 65% relative humidity (RH)

Table III

68% linseed / pentaerythritol / phthalic anhydride alkyd, unpigmented and used in the form of a 40% solution in white spirit, tested for drying properties at 25 ° C and 100 ° C and for storage stability at 25 ° C

Table IV

78% linseed / pentaerythritol / phthalic anhydride-Akyd, unpigmented and used in the form of a 65% solution in white spirit to carry out drying tests at 22 ° C and 100 ° C

Claims (6)

1. Mix of

• (A) an aluminum compound of the general formula (RO) _x AlAB _{(2- x)} where x is the number 0, 1 or 2, R is an alkyl, substituted alkyl, alkoxyalkyl, cycloalkyl, aryl, aralkyl, alkaryl -, Aminoalkyl or glycol half ester group, A and B, which may be the same or different from one another, denote the same group as RO or a β- ketocarboxylic acid ester residue, a half ester residue, a diester residue, a carboxylic acid or aminocarboxylic acid residue, and
• (B) at least one mole per g-atom of aluminum of an unstable monofunctional reactant and optionally
• (C) an inert diluent,

characterized in that the reactant (B)

• (B1) water,
• (B2) aqueous hydrogen peroxide,
• (B3) an organic hydroperoxide

or a mixture of an organic Monohydroxy compound of the formula R²OH, wherein R² is a substituted or unsubstituted C₁ to C₁₈ alkyl or cycloalkyl means with one of the components (B1), (B2) or (B3).   2. Mixture according to claim 1, characterized in that the monohydroxy compound of the formula R²OH Ambient temperature is volatile. 3. Mixture according to claim 1 or 2, characterized characterized in that the organic hydroperoxide (B3) is t-butyl hydroperoxide or cumene hydroperoxide. 4. Use of a mixture according to one of the claims 1 to 3 for the production of an air drying Paints based on an oil-modified alkyd resin or an oleoresin medium.